8.

Petrochemical Product from

Butane-Butylene

1
 Butane

n-butane

• Also known as n-butane isobutane

• Unbranched alkane
• Molecular Formula: C4H10
• Present only 1 isomer, isobutane
• Colorless, odorless, highly flammable
2
 Butane
Industrial Application:
• Fuel for cooking and camping
• Commercial LPG (blended with propane gas)
• Household refrigerants, replacement on halo-methane (CCl4)
• Fuel for cigarette lighter
• Feedstock for steam-cracking process → basic petrochemical
product (such as propylene)

3
 Butane
Properties of Butane

Properties Value
Molecular Weight 58.1
Boiling point 31°F
Solubility Slight
Specific Gravity 0.6 (Liquid at 31°F)
Vapor Pressure 2.05atm
Freezing Point -217°F
Physical State Gas
Source: NIOSH Pocket Guide

4
 Butylene

Isobutene 1-Butene

Cis-2-butene Trans-2-butene

5
 Butylene
• Also known as butene
• Molecular Formula: C4H8
• Present 4 isomers: Isobutene, 1-butene, cis-2-butene
and trans-2-butene
• Colorless gas
• Obtained through catalytic cracking of long chain
hydrocarbons (extracted by fractionation distillation)
• Also can obtained by dehydrogenation of butane
6
 Butylene
Industrial Application:
• Monomer for polybutene
• Acetic acid and acetic anhydride
• Metyl ethyl ketone (MEK)
• Maleic anhydride (MA)
• 2-butanol
• Polymer grade propylene

7
 Butylene
Properties of Butylene
Properties Value
Molecular Weight 56
Boiling point -6.3°C
Solubility Insoluble
Specific Gravity Not Available
Vapor Pressure 37psia at 70°F
Freezing Point Not Available
Physical State Gas
Source: NIOSH Pocket Guide

8
 Butadiene
• Colorless, mild aromatic odor,
reactive, flammable gas

• Soluble in alcohol and ether;

1,3-butadiene
insoluble in water
• Readily polymerizes (especially if oxygen present)
• Obtained by steam cracking of light olefins
• Other sources: catalytic dehydrogenation of butane
and butylene & dehydration of 1,4-butanediol

9
 Butadiene
Industrial Application:

• Synthetic rubber (SBR and nitrile rubber)

• Starting material of nylon 66 (adiponitrile)
• Ingredient in rocket fuel (butadiene-
acrylonitrile polymer)
• Solvent (butanediol and sulfolane)

10
 Butadiene
Properties of Butadiene
Properties Value
Molecular Weight 54.1
Boiling point 24°F
Solubility Insoluble
Specific Gravity 0.65 (Liquid at 24°F)
Vapor Pressure 2.4atm
Freezing Point -164°F
Physical State Gas
Source: NIOSH Pocket Guide

11
C4 Industrial Petrochemical Processes

12
C4 Industrial Petrochemical Processes

13
 Oxidation of Butane

1. Acetic Acid

• Noncatalytic:
 Temperature: 360-450°C
 Pressure: 7 atm
 Low selectivity: 33% formaldehyde, 31%
aceltaldehyde, 20% acetone & 12% mixed
solvent

14
 Oxidation of Butane
• Celanese Process (Catalytic):

C4H10 + 2½ O2 → 2 CH3COOH + H2O

 Temperature: 150°C
 Pressure: 55 atm
 Catalyst: Peroxide form of Manganese, Cobalt or
Chromium
 The butane is kept in liquid state as the reaction
run

15
 Oxidation of Butane
 2 categories of by-product from the reaction:

 Below water boiling point: ethyl acetate, MEK, vinyl

ketone and etc
 Above water boiling point: formic acid, propionic,
acrylic, butyric and succinic acids and etc

 Formation of by-product depend on the types of

catalyst used.
 Some of the by-products are commercially
valuable
 Acetic acid is widely used as protic solvent and
vinegar production
16
 Oxidation of Butane
Acetic Acid Production from Acetaldehyde

CH3CHO + ½O2 → CH3COOH

 Oxidation of acetic acid

 Temperature: similar with Celanese Process
 Pressure: similar with Celanese Process
 Catalyst: similar with Celanese Process
 Yield: >95%
 By-product: ethyl acetate, formic acid and
formaldehyde (separate by distillation method)
17
 Oxidation of Butane
2. Maleic Anhydride

Maleic anhydride

• Produce via Monsanto Process and Dupont Process

• Replacement process of catalytic benzene oxidation
• Precursor for 1,4-butanediol production, synthesis of
fumaric and tartaric acid.

18
 Oxidation of Butane
Monsanto Process

 Temperature: 400-480°C
 Pressure: 0.3-0.4Mpa
 Catalyst: Vanadium Phosphorus
Oxide (VPO)
 Exothermic process
19
 Oxidation of Butane

Remark:

Source: Petrochemical Handbook

20
 Oxidation of Butane
 n-butane and air are fed to a multitube
fixed-bed reactor, which is cooled with
molten salt.
 The exit gas stream is cooled, and crude
maleic anhydride is absorbed.
 The maleic anhydride is then recovered
from the solvent in the stripper.
 Maleic anhydride is further purified using a
proprietary solvent purification system.
21
 Oxidation of Butane
DuPont Process

 Temperature: 500°C
 Pressure: 1 atm
 Catalyst: Vanadium Phosphorus Oxide (VPO)
 Exothermic process
 The catalyst provide the oxygen needed in this
process
 The selective oxidation of n-butane to maleic
anhydride involves a redox mechanism
 The removal of eight hydrogen atoms as water and
the insertion of three oxygen atoms into the butane
molecule occurs.
22
 Oxidation of Butane
DuPont Process

Process is carried out in

a circulating fluidized bed-
reactor.

Solids flux in the rizer-

reactor is high and the
superficial gas velocities
are also high, which
encounters short residence
times usually in seconds.

Source: Haggin J., 1995

23
 Oxidation of Butylene
1. Acetic Acid

 Temperature: 270°C
 Pressure: 1 atm
 Catalyst: Titanium Vanadate
 Yield: 70%
 By-product: Carbon oxide & maleic anhydride
 Vapor-phase catalytic process
24
 Oxidation of Butylene
2. Metyl Ethyl Ketone (MEK)

 Temperature: 130°C
 Pressure: 3 atm
 Catalyst: Wacker Catalyst (PdCl2/CuCl2)
 Yield: 88%
 By-product: Carbon oxide & maleic anhydride
 Liquid-phase catalytic oxidation process
25
 Oxidation of Butylene

 MEK
A colorless liquid with a sweet, but sharp odor.
Often found dissolved in water or as a gas in the
air.
Manufactured in large amounts for use in paints
and glues because it rapidly evaporates and will
dissolve many substances.
A natural product made by some trees and is
found in some fruits and vegetables.
26
 Oxidation of Butylene
3. Maleic Anhydride

 Temperature: 400-440°C
 Pressure: 2-4 atm
 Catalyst: Oxide mixture of molydenum, vanadium
and phosphorus
 Yield: 45%
 Maleic anhydride acted as an intermediate to
produce malathion and maleic hydrazine

27